Process for preparing higher alkyl esters of methacrylic acid



United States PatentO PROCESS FOR PREPARING HIGHER ALKYL ESTERS F METHACRYL'IC ACID William T. Stewart and Alfred Goldschm'idt, El Cerrito, Calif., assignors to California Research Corporation, San Francisco, Calif., a corporation of Delaware N6 Drawing. Application September as, 1956 Serial No. 612,873

3 Claims. (Cl. 260-486) The present invention is concerned with a novel process for preparing polymerizable unsaturated esters. More particularly, the invention is directed to a superior new process for preparing higher aliphatic esters of n p-unsaturated monocarboxylic acids which are polymerizable.

Polymerizable higher aliphatic esters of c p-unsaturated monocarboxylic acids are useful in the preparation of oilsoluble polymeric additives for lubricants and fuels. These polymerizable esters may be produced by the direct esterification of an esp-unsaturated monocarboxylic a'cid. However, a preferredrnethod for preparing such esters has been by the so-called ester'interchange reaction, or alcoholysis, of a lower alkyl ester of m, 3-unsaturated monocarboxylic acid with a higher aliphatic .al'coholor ether alcohol. Reactions of thistype customarily employ an acidic esterification catalyst such as sulfuric acid in combination with a polymerization inhibitor such as hydroquinone to inhibit undesirable polymerization of the unsaturated esters;

In the ester interchange or alcoholy'sis method of preparing higher aliphatic esters of a,fi-unsaturated mono carboxylic' acids, several problems have been encountered. The yields of higher aliphatic esters have not been satisfactory due to the formation 'of undesirable polymers. Furthermore, emulsions are often formed which are difiicult to separate and result in loss of product.

It has been suggested that the problem of excessive polymerization and emulsionformation might be solved by the introduction of oxygen-containing gases into the ester interchange reaction of the aliphatic alcohol or ether alcohol with the lower alkyl ester of the unsaturated monocarboxylic acid. This method has not been completely eifective. Furthermore, the introduction of oxygen into the process is objectionable, since there is considerable danger=of violent explosions due to, the presence of free oxygen in combination with combustible. materials.

In the co-pending application of Paul K; Mulvany,

William W. West and Alfred Goldschmidt entitled Preparation of Unsaturated Esters, Serial No. 612,814, filed'September 28, .1956, it is shown that higher aliphatic esters of 01, 3-111'1S3il113i6d monocarboxylic acids suitable for the production of polymeric additives can be readily prepared inexcellent yields without the formation of excessiv'e polymer and/or emulsions by a process which comprises reacting a lower alkyl ester of an] o e-unsaturated monocarboxylic acid with a member of the group consisting of higher aliphatic monohydric alcohols and aliphatic ether alcohols in the presence of a basic esterification catalyst and a polymerization inhibitor, the molar equivalent ratio of polymerization. inhibitor to catalyst being greater than 1. y I

It has now been found in accordance withthepresent invention that substantial savings and improvement of the, quality of the product in. the above'process may be effected by the use of a particular polymerization in-. hibitor, namely, quinone, without impairment ofiother 2,891,991 Patented June 23, 1959 benefits of the process such as the avoidance of excessive polymer formation and/ or emulsions.

While in the previous method the polymerization inhibitor was required in a molar equivalent excess over the amount of basic esterification catalyst, the quinone polymerization inhibitor of this process is surprisingly eiiective in concentrations which are to of those previously used with conventional polymerization inhibitors such as hydroquinone. Since the use of quinone specifically as a polymerization inhibitor in combination with a basic esterification catalyst has apparently not been contemplated prior to the present invention, it is altogether unexpected that this inhibitor in particular would provide such a substantial saving in the amount of inhibitor required for the reaction. Since the polymerization inhibitors for such reactions as a class are a considerable part of the over-all cost, this saving in the amount of catalyst is a great economic advantage.

The use of less polymerization inhibitor such as the quinone in accordance with this invention has another important advantage in that the higher aliphatic esters of a ti-unsaturated monocarboxylic acids produced in the reaction are more easily purified than products heretofore obtained in processes using large amounts of polymerization inhibitor. All of this polymerization inhibitor must be removed before the product can be used in the preparation of polymers.

Briefly stated, the improved new process of this invention for preparing polymerizable higher aliphatic esters of cap-unsaturated monocarboxylic acids comprises reacting a lower alkyl ester of an tr e-unsaturated monocarboxylic acid with a member of the group consisting of higher aliphatic monohydric alcohols and aliphatic ether alcohols in the presence of a basic esterification catalyst and quinone as polymerization inhibitor.

The lower alkyl ester of cap-unsaturated monocarb'oxylic acid of the process preferably contains from 1 to 4 carbon atoms in the alkyl group. The more suitable esters of this type have the general formula wherein R R and R are the sameor different members of the group consisting of hydrogen'atoms and alkyl groups of from 1 to 4 carbon atoms and R is an alkyl group of from 1 to 4 carbon atoms. Esters of this type include the methyl, ethyl, propyl, isopropyl, butyl, sec.- butyl and tert.-butyl esters of anti-unsaturated monocarboxylic acids such as acrylic, methacrylic, crotonic, tiglic, angelic, a-ethylacrylic, a-methylcrotonic, ot-ethylcrotonic, fl-ethylcrotonic, rx-butylcrotonic, hydrosorbic, u-ethylhydrosorbic and u-propylhydrosorbic acids and the like as well as mixtures thereof. For present purposes, a more suitable group of esters of the foregoing type. is composed of "esters of acids containing a total offrom about 3 to '8 carbon atoms in the molecule. The methyl and ethyl esters of acrylic andmethacrylic acids, particularly methylmethacrylate, constitute preferred species on the basis of availability and effectiveness in the process of'the invention.

The higher aliphatic monohydric alcohols suitably con tain a higher number of carbon atoms than. the number of carbon atoms in the. alkyl group of the lower alkyl' ester of a ti-unsaturated monocarboxylic acid as described above. Preferablyflhe alcohol contains at'least' 5 carbon atoms. Still more preferred are those h'aving from 8? to 30 carbon atoms. These alcohols are most effective in the reaction 'of the invention and are particularlysuih able in the production of esters which are especiallyde+ sirable for preparing polymeric 'additivesf ofthe afore mentioned types.- 1 I The higher aliphatic monohydric alcohols may be of a primary, secondary or tertiary nature. For present purposes, primary and secondary alcohols, and particularly the primary alcohols, are preferred. Preferably, the alcohols are branched or straight-chain in nature, although cyclo-aliphatic groups are not precluded.

Aliphatic monohydric alcohols illustrative of the foregoing type are n-pentanol, Z-pentanol, cyclopentanol, n-hexanol, cyclohexanol, Z-ethylhexanol, dodecanol, l-pentadecanol, octadecanol, S-ethyldocosanol, triacontanol and the like. The straight-chain and branchedchain primary alcohols which contain from to carbon atoms are particularly preferred for present purposes.

The aliphatic ether alcohols are alkyl ethers of aliphatic polyhydric alcohols such as the glycols, polyalkylene glycols and other polyatomic alcohols, including glycerol, pentaerythritol, etc. Particularly suitable glycol monoalkyl ethers and polyalkylene glycol monoalkyl ethers have the formula wherein the R s are 1,2-alkylene radicals of 2 to 7 carbon atoms each, n is an integer of at least 1 and R is an alkyl group of from 1 to 18 carbon atoms. The preferred ether alcohols for present purposes are the poly- 1,2-alkylene glycol monoalkyl ethers of the type derived from polymerization of ethylene oxide or 1,2-propylene oxide or mixtures thereof in which aliphatic monohydric alcohols of from 1 to 18 carbon atoms are used as initia tors, said ether alcohols having molecular weights between about 106 and 2,000.

Illustrative polyalkylene glycol monoalkyl ethers of the foregoing type include:

Polyethylene glycol monododecyl ether mixtures having average molecular weights of 200, 400, 1000, 1540, 2000 or 10,000.

Poly-1,2-propylene glycol monododecyl ether mixtures having average molecular weights of 425, 1025 or 10,000.

The improved new process of the present invention is particularly adaptable to the use of aliphatic monohydric alcohols and for that reason those materials as described above are presently preferred.

As their name indicates, the basic esterification catalysts of the process are esterification catalysts Which have the properties of a base. Such catalysts, for present purposes, are preferably alcoholates of a metal such as sodium, potassium, lithium, calcium, magnesium or aluminum. The lower alcoholates of sodium or potassium, such as sodium methylate or sodium methoxide, as it is sometimes referred to, potassium ethylate and other similar alcoholates containing not more than 7 carbon atoms, and particularly 2 or less, are still more preferred. Sodium methylate or sodium methoxide is presently the most preferred on the basis of availability and elfectivity.

In the reaction, the lower alkyl ester of the ozfi-HH- saturated monocarboxylic acid is desirably present in a molar excess over the amount of the higher aliphatic monohydric alcohol or aliphatic ether alcohol. The molar ratio of ester to aliphatic alcohol is preferably within the range of from about 3 :1 to about 12:1. Molar ratios of lower alkyl ester to aliphatic monohydric alcohol of about 3:1 to about 5:1 are presently the most preferred for optimum conversions. Any excess lower alkyl ester from the reaction is conveniently recovered for reuse.

Sufficient basic esterification catalyst is employed to promote the ester interchange or alcoholysis of the lower alkyl ester of the 00,}3-1111Sfl'tll13t6d monocarboxylic acid with the higher aliphatic monohydric alcohol or the aliphatic ether alcohol. From about 10 to about 50 mole percent of the catalyst on the basis of the higher aliphatic monohydric alcohol or aliphatic ether alcohol is preferably employed. About 35 mole percent of catalyst is presently the most preferred for consistently high conversions, particularly in the case of sodium methylate catalyst and aliphatic monohydric alcohols of from 10 to 20 carbon atoms.

The quinone polymerization inhibitor may be present in any desired amount suificient to inhibit polymerization of the unsaturated compounds in the reaction according to the process of this invention. As previously mentioned, a particularly desirable feature of the present process lies in the fact that the quinone polymerization inhibitor is unexpectedly effective in small amounts. Thus, the molar equivalent ratio of the polymerization inhibitor to the basic esterification catalyst may be less than 1 for present purposes, whereas it formerly appeared that all polymerization inhibitors were required in a molar equivalent ratio greater than 1. Since the polymerization inhibitor is one of the more expensive materials in this type of process and since removal of the polymerization inhibitor is necessary in normal purification procedures prior to any polymerization, it will be appreciated that a preferred embodiment of this invention lies in the use of quinone inhibitors in a molar equivalent ratio of inhibitor to basic esterification catalyst of less than 1 and preferably of not more than 0.5. With these small amounts of quinone polymerization inhibitor, a great saving in over-all expense of the reaction is accomplished and the purification procedures are considerably simplified.

In the present description the terms molar and equivalent are used with respect to the catalyst and the quinone polymerization inhibitor in their commonly accepted sense, molar meaning the molecular weight of the compound expressed in grams and equivalent" meaning the molecular weight of the compound divided by the valency of its principal radicals. For example, sodium methylate has a molecular weight of roughly 55 and the valence of its principal radical is one. Thus, a molar equivalent of sodium methylate is 55 grams. Quinone, on the other hand, has a valence of 4, due to its 2 double-bonded oxygens, and a molecular Weight of approximately 108. Therefore, dividing 108 by 4 gives a molar equivalent of quinone of 27 grams which is approximately one-half the Weight in this example of the sodium methylate catalyst. Accordingly, the use of any weight of quinone inhibitor less than one-half the weight of sodium methylate catalyst will give a molar equivalent ratio of inhibitor to catalyst of less than 1. Weight ratios of quinone to sodium methylate catalyst of 0.5:1 to 0.01:1 and, more particularly, 0.2:1 to 01:1 are very suitable for present purposes.

The reaction may be conducted at any temperature at which ester interchange or alcoholysis occurs. Preferably, the reaction temperature should not exceed 265 F., since undesirable polymerization may be thermally initiated at higher temperatures. Still more preferred are reaction temperatures in the range from about F. to about 250 F. with temperatures of from about 210 to about 215 F. being considered the most satisfactory from the standpoint of optimum conversions and suppression of undesirable side reactions.

Atmospheric, superatmospheric or subatmospheric pressures may be employed in the reaction. Pressures less than atmospheric are generally preferred to permit proper control of the reaction temperatures within the limits described above. Pressures equal to about 300 able to add polymerization inhibitor to the lower alkyl ester at this point to prevent its polymerization.

The following examples are offered in further illustration of the invention. Unless otherwise specified, the

to about 700 mm. of mercury are particularly suitable, 5 Proportions are given on a weight basis although pressures as low as about 50 mm. of mercury may be conveniently utilized, especially in the final stages of the reaction where excess lower alkyl ester of EXAMPLE I the p lunsaturated molrliocarboxylic acid maydbe strlpped 600 grams of methyl methacrylate (6 moles) and or dlsnied f frqm t e Ramon 1 10 grams of quinone (0.36 molar equivalent) are charged Sufficrent time is permitted in the reaction to insure to a reaction Vessel q pp with Stirring means and the desired conversion of lower alkyl ester of a,B-unsatreflux column The mixture is Stirred at room urated monocarboxylic acid to the higher aliphatic ester. Pera'ture to dis'solve the quinone 400 grams of tridecyl from aboui 2 about 12 hours Teacnon tune alcohol (2 moles) is charged to the mixture. 20 grams 1s sufficient. Reaction times of from about 4 to 10 hours of Son d Sodium methylate- (0.36 molar equivalent) is are g g preferred g conslstenffliy 5 converslonsi then charged The mixture is heated under refluxing con T e cru e reaction pro net is pur' e y conventiona procedures to give the desired higher aliphatic ester of ditions, during which the reaction temperature rises steada,,B-unsaturated monocarboxylic acid. Excess lower al- Whgn temper ature of 215 1s reached m kyl ester may be stripped off by vacuum distillation. 2O g?' 1S atPPhed to the Feactlon i to F Following this, the stripped crude product may be washed am ure as a maxlmume reactlon 15 with an alkaline solution such as an aqueous solution of cemplete h I a sodium hydroxide or sodium carbonate to extract the The Ieactlon mlxture dlstlued up to at a polymerization inhibitor. After this, the crude reaction Pressurte d tg i 50 1 t l r l i ly tOtSlZIIP (inf exgessL product is washed with an aqueous salt solution of, for Pmeac 6 me Y 1116 'y a e 5 PP P examlple, SOdlugl chloride or sodium sulfate, to remove fi d z v i fl'i u s s gd? Pgy gir gd l s gn any ase or ot er impurities remaining. 6 aq eo 111m 1 0 e 50 u 1 it As mentioned previously, purification of the crude re- Yvlth a 10% Sodlum chlqrlde Solutlonfl pp Phase a ti product of th present i ti i tl i in the separatory vessel is recovered and dried over calproved due to the fact that there need be only small W Chlorlde- The Yield of trldecyl methacl'ylate pamounts of the quinone polymerization inhibitor present. pfoXlmately 93% of theoretical, based the y This fact, plus the fact that the products of this process 'g t0 the @actlolh V y little emulslon, are unusually resistant to the formation of difiicultly sepa ntmg to 2% or less, 18 formed the P I P arable emulsions greatly simplifies the over-allpurifica- Th6 de ta11S 0the1 6XamP1eS 111 addltlofl' f the hon procedure and gives the present process a s gnificant above which are illustrative of the process of this inven- %dV3.I1tag61OV i-{ kprocesfses of a similar type WlllCh have 2 01 1 aretzllmmaflled 1H l follovglng table. E 2 2 1 212 een emp oye ereto ore. o ow e same genera proce ure as on me in e If desired, solvents may be used in the process of the foregoing P These add'itiqniill pl s lud invention to facilitate the handling of reactants and for comparison the use of other inhibitors such as phenylmaintenance of reaction conditions. Hydrocarbon sol- 40 u-naphthylamine and hydroquinone. Also included are vents such as toluene or xylene are particularly suitable representative higher alpihatic monohydric alcohols and for reaction and/ or purification steps. aliphatic ether alcohols.

Table Mole Mole Yield Example Moles Ratio, Percent Molar Equiv. Reaction Max. Percent No. Alcohol Ester: Catalyst Ratio ofInhib.: Time, Temp., Bascdon Remarks Alcohol Based on Catalyst Hrs. F. Alcohol Alcohol 20. 4 0.20 (Q) 5 5 250 97 N prmal reaction-no emulsion prob- 6131. 9.2 0.50 (PAN)--- 40 220 None Polymerization. 22.2 0.34 (Q) 5 225 94 Niiglal reaction-no emulsion prob- 16.6 0.22 (Q) 5% 225 95 150. 18.5 0. 5% 235 98 Do.

9.2 e 1 195 None Polymerization. 24. 0 0 4 (Q).- 5 230 97 N inmal reactionno emulsion probem. 31.5 0.12 (Q) 6% 240 94 D0.

A-Tridecanol.

BMixed 01 -0 8 alcohols containing 1.0 mole tridecanol and 0.7 mole octadccanol. C-Tridecanol-initiated polyethyleneglycol having an average molecular weight of approximately 440.

HQ,Hydroquinone. Q-Quinone. PANPhenyl-a-naphthylamine.

In the process an azeotropic mixture is ordinarily distilled off during the reaction. This mixture contains a portion of the lower alkyl ester of t p-unsaturated monocarboxylic acid, along with the lower aliphatic alcohol by-product of the alcoholysis reaction. The lower alkyl ester of the a,/3-unsaturated monocarboxylic acid is conveniently recovered from the azeotropic mixture by washing with an aqueous solution, for example, brine, to separate out the more miscible lower aliphatic alcohol. The lower alkyl ester, along with remaining excess lower alkyl ester distilled off in the final stages of the process, is thus The data provided by the above examples show that the present process for preparing higher aliphatic esters of a,fi-unsaturated monocarboxylic acids requires only a small fraction of the quinone polymerization inhibitor compared to similar processes utilizing hydroquinone polymerization inhibitor. Whereas in previous processes it is considered necessary to use hydroquinone polymerization inhibitor in a molar equivalent ratio of inhibitor to basic catalyst which is greater than 1, in this process, the quinone polymerization inhibitor is effective in ratios as low as 0.02. The advantages in the use of available for reuse in the process. Ordinarily, it is desir- '75 quinone as a polymerization inhibitor in accordance with this invention are obtained without the loss of any of the other advantages which are derived from the use of basic esterification catalyst and polymerization inhibitor. No emulsion problems are encountered, and the yields of product are excellent.

We claim:

1. A process for preparing higher alkyl esters of methacrylic acid Which comprises reacting methyl methacrylate with a primary alkanol of from 10 to 20 carbon atoms in the presence of sodium methylate basic esterification catalyst and quinone polymerization inhibitor, the molar equivalent ratio of polymerization inhibitor to catalyst being less than one and said sodium methylate basic esterification catalyst being present in an amount of about 10 to about 50 mol percent based on the amount of primary alkanol.

2. A process for preparing higher alkyl esters of methacrylic acid which comprises reacting methyl methacrylate with tridecanol in the presence of sodium methylate basic esterification catalyst and quinone polymerization inhibitor, the molar equivalent ratio of polymerization inhibitor to catalyst being less than one and said sodium methylate basic esterification catalyst being present in an amount of about 10 to about 50 mol percent based on the amount of tridecanol.

3. A process for preparing higher alkyl esters of methacrylic acid which comprises reacting methyl methacrylate With a mixture of 1.0 mol tridecanol and 0.7 mol octadecanol in the presence of sodium methylate basic esterification catalyst and quinone polymerization inhibitor, the molar equivalent ratio of polymerization inhibitor to catalyst being less than one and said sodium methylate basic esterification catalyst being present in an amount of about 10 to about 50 mol percent based on the amount of mixed tridecanol and octadecanol.

References Cited in the file of this patent UNITED STATES PATENTS 2,129,667 Barrett et al Sept. 13, 1938 2,129,694 Izard Sept. 13, 1938 2,129,722 Woodhouse Sept. 13, 1938 2,396,434 Rehberg et al. Mar. 12, 1946 OTHER REFERENCES Kice: I. Am. Chem. Soc., 76 (1954), 6275-6.

Frank et al.: J. Am. Chem. Soc., 68 (1946), 908.

Riddle: Monomeric Acrylic Esters (1954), pp. 186-8. 

1. A PROCESS FOR PREPARING HIGHER ALKYL ESTERS OF METHACRYLIC ACID WHICH COMPRISES REACTING METHYL METHACRYLATE WITH A PRIMARY ALKANOL OF FROM 10 TO 20 CARBON ATOMS IN THE PRESCENCE OF SODIUM METHYLATE BASIC ESTERIFICATION CATALYST AND QUINONE POLYMERIZATION INHIBITOR, THE MOLAR EQUIVALENT RATIO OF POLYMERIZATION INHIBITOR TO CATALYST BEING LESS THAN ONE AND SAID SODIUM METHYLATE BASIC ESTERIFICATION CATALYST BEING PRESENT IN AN AMOUNT OF ABOUT 10 TO ABOUT 50 MOL PERCENT BASED ON THE AMOUNT OF PRIMARY ALKANOL. 